JP2003292825A - Colored metallic pigment and resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored metallic pigment which can give various colors, exhibits an excellent finished appearance and an excellent weather resistance, and is produced by a safe and simple production method. <P>SOLUTION: The colored metallic pigment comprises metallic particles and a single- or multi-layer coating film coating the surfaces of the metallic particles, and at least one layer of the single- or multi-layer coating film is a cobalt coating film composed of an anhydrous oxide film containing cobalt as an element. The cobalt coating film prefarably contains at least one compound selected from the group consisting of CoO, Co<SB>2</SB>O<SB>3</SB>, Co<SB>3</SB>O<SB>4</SB>, nCoO-mAl<SB>2</SB>O<SB>3</SB>and nCoO-mSiO<SB>2</SB>(wherein n and m are each a positive real number). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored metal pigment. More specifically, the present invention relates to colored metallic pigments with a single-layer or multi-layer coating. The present invention also relates to a resin composition containing the above colored metal pigment.

[0002]

2. Description of the Related Art A coating film formed by using a metallic paint shows a glittering design by reflecting incident light from the outside with a scaly metallic pigment contained in the coating film. In addition, the reflection of light, in combination with each color tone of the coating film, provides a unique appearance with excellent design.

Taking advantage of these characteristics, metallic pigments containing aluminum flakes as base particles are mainly used for metallic finishes such as automotive finish, plastic finish, printing ink and resin composition molding. There is.

Further, in recent years, with the diversification of consumers' tastes, highly bright metallic pigments having various colors such as red, green, and purple have been desired. However, since aluminum flakes are originally achromatic and are pigments exhibiting a silver-white luster, the above-mentioned consumer demand cannot be satisfied as they are.

Therefore, many attempts have been made in order to solve these problems and satisfy consumers' demands for various colors. For example, JP-A-58-141248
Japanese Patent Publication No. 5-508424, Japanese Patent Laid-Open No. 1-3084
Japanese Patent No. 15470, Japanese Patent Application Laid-Open No. 9-40885, Japanese Patent Application Laid-Open No. 9-59532, Japanese Patent Application Laid-Open No. 9-124973 and the like disclose techniques relating to colored metal pigments in which a color pigment is attached to metal particles. .

Here, as a method for producing these colored metallic pigments, the colored pigments are attached to the surface of the metal particles,
A method of coating with a film made of a polymer composition is generally used. Further, as the coloring pigment used for these colored metal pigments, diketopyrrolopyrrole-based, quinacridone-based, dioxazine-based, isoindolinone-based, condensed azo-based, slene-based, perinone-based, perylene-based, phthalone-based, phthalocyanine-based Organic pigments such as, or inorganic pigments such as iron oxide and carbon black are generally used.

However, these colored metallic pigments have a problem that the colored pigments adhered to the surface of the metallic particles are easily deteriorated due to the reflection of light on the surface of the metallic particles. In order to solve this, it is unavoidable to select a pigment having relatively excellent light resistance such as phthalocyanine green, phthalocyanine blue, iron oxide, etc., and there is a limit to the designability of the obtained colored metal pigment at present. .

On the other hand, Japanese Patent Laid-Open No. 63-161063,
JP-A-4-28771, JP-A-2001-3166
Japanese Patent Application Laid-Open No. 09, etc. discloses a technique relating to a colored pearlescent pigment that gives an interference color by forming a film of silicon oxide, titanium oxide, metal or the like on the surface of a pearlescent pigment such as mica. However, since these colored pearlescent pigments have a small hiding power, there is a drawback that the base cannot be sufficiently covered even when blended in paint or ink.

In order to solve these problems, there are some techniques relating to a colored metal pigment obtained by coloring the surface of metal particles having high hiding power by coating with an interference film such as silicon oxide, aluminum oxide or titanium oxide. It is disclosed.

For example, JP-A-1-110568 and JP-A-2-669 disclose methods of depositing titanium oxide on the surface of metal particles by a sol-gel method. However, with this method, a colored metal pigment with high saturation cannot be obtained, and since the titanium oxide layer has no choice but to become an anatase phase with high activity, deterioration of the resin is promoted when it is blended in a paint or the like. However, there is a problem that the weather resistance is lowered.

Further, Japanese Patent Application Laid-Open No. 56-120771,
JP-A-1-311176 and JP-A-6-32994
The publication discloses a method of obtaining a composite phase of iron oxide, titanium oxide, metal oxide, etc. and carbon, metal, metal oxide, etc. on the surface of metal particles by a vapor phase method. But,
When using the gas phase method, it is necessary to fluidize the metal particles, supply the precursor of the metal oxide, and heat-precipitate it, but it requires a special device and the risk of dust explosion of the metal particles. The precursors of metal oxides are large and many of them are highly toxic, so that they are difficult to handle.

Further, in JP-A-8-209024, a colorless coating layer having a refractive index of 1.8 or less and 2.0
A technique relating to a multilayer coated metal pigment based on a two-layer structure with a selective absorption layer having the above refractive index is disclosed. However, this technique discloses a method of forming a metal oxide layer on the surface of metal particles by a vapor phase method or a method of hydrolyzing a metal compound in a solution, but the vapor phase method has the above-mentioned drawbacks. However, in the method of forming a metal oxide layer by hydrolyzing a metal compound in a solution, the hydrolysis reaction is carried out in a basic or acidic atmosphere containing a large amount of water, so that the metal particles and the water are not treated during the treatment process. There is a problem in that there is a possibility that a reaction with the metal particles may occur, causing agglomeration of metal particles and a runaway reaction.

Further, JP-A-51-150532 and JP-A-63-15861 disclose a method of depositing a metal oxide layer by mixing aluminum powder, a metal salt and a chelate compound. . However, JP-A-5
Since the method described in JP-A-1-150532 is carried out in an aqueous solution, there is a great risk that the aluminum powder reacts violently with the processing liquid, and a large amount of hydrogen gas is generated, a remarkable heat generation due to a runaway reaction, and aluminum powder This is not practical because problems such as aggregation may occur.

Even with the method described in JP-A-63-15861, it is difficult to avoid the above problems caused by the violent reaction between the aluminum powder and the treating liquid, and the reaction is acidic to medium. Since it is carried out in a region where the metal compound is present, precipitation of the metal compound does not occur efficiently, and there is a problem that a large amount of unreacted metal salt remains.

Further, since the metal oxide layer obtained by these methods is a hydrated film containing water, it has poor adhesion to a binder such as a resin contained in the paint, so that the metal oxide layer is peeled off or has moisture resistance over time. It tends to cause problems such as deterioration. Further, the above-mentioned metal oxide layer is a hydrated film, so that the film tends to be incomplete, and there is a problem that a good color is not often obtained.

[0016]

As described above, it is strongly desired to develop a colored metal pigment which can realize various colors, is excellent in finished appearance and weather resistance, and can be manufactured by a safe and simple manufacturing method. However, the technology relating to such a colored metal pigment is not yet known.

Based on the above situation, an object of the present invention is to provide a colored metal pigment which can realize various colors, is excellent in finished appearance and weather resistance, and can be manufactured by a safe and simple manufacturing method. is there.

Another object of the present invention is to provide a resin composition which can realize various colors, is excellent in finished appearance and weather resistance, and can be manufactured by a safe and simple manufacturing method.

[0019]

In order to achieve the above-mentioned object, the inventors of the present invention can safely and simply form a single-layer or multi-layer coating containing different kinds of metal elements on the surface of metal particles as base particles. The idea that the interference effect of light should be utilized by providing such a method was conducted, and earnest studies were conducted on many kinds of metal elements.

After trial and error, the inventors of the present invention can safely and simply provide an anhydrous oxide film containing cobalt as an element on the metal particles serving as the base particles by using a specific manufacturing method. As a result, they have found that a colored metal pigment having an excellent appearance can be obtained.

Furthermore, the inventors of the present invention, by using a specific manufacturing method, further provide an oxide film or an acid containing a different metal element such as titanium outside the anhydrous oxide film containing cobalt as an element. It has been found that a nitride film can be provided safely and simply, and colored metal pigments having a wider variety of colors can be obtained.

The inventors of the present invention can safely and simply use a film containing aluminum, silicon, cerium or the like as an element on the outside of the titanium-containing oxide film or oxynitride film by using a specific manufacturing method. Can be provided,
The present invention has been completed by finding that the problem of weather resistance that occurs in an oxide film or an oxynitride film containing titanium as an element can be overcome.

That is, the colored metal pigment of the present invention is a colored metal pigment provided with metal particles and a single-layer or multi-layer coating for coating the surface of the metal particles. At least one layer of the coating film is a colored metal pigment, which is a cobalt coating film made of an anhydrous oxide film containing cobalt as an element.

Here, the cobalt coating is CoO, C
o ₂ O ₃ , Co ₃ O ₄ , nCoO.mAl ₂ O ₃ , nCoO.
It is preferable to contain a compound having a composition represented by one or more selected from the group consisting of mSiO ₂ (n and m are any positive real numbers).

The cobalt coating has a thickness of 0.01-1.
It is desirable to have a film thickness in the range of μm. Furthermore, this elemental cobalt is based on 100 parts by mass of the metal particles.
It is recommended to be contained in the cobalt coating in the range of 0.5 to 50 parts by mass.

The colored metallic pigment of the present invention is preferably provided with a silicon-aluminum coating formed of an oxide film containing silicon and / or aluminum as an element inside the cobalt coating.

Here, the silicon-aluminum coating is
Al ₂ O ₃ , SiO ₂ , SiO, nSiO ₂ · mAl ₂ O
It is desirable to contain a compound having a composition represented by one or more selected from the group consisting of ₃ (n and m are any positive real numbers).

The silicon-aluminum coating is
It is recommended to have a film thickness in the range of 0.01-1 μm. Furthermore, this silicon and / or aluminum is 0.01 to 0.01 parts with respect to 100 parts by mass of the metal particles.
It is preferably contained in the silicon-aluminum coating in an amount of 50 parts by mass.

The colored metal pigment of the present invention is preferably provided with a molybdenum-phosphorus coating film, which is an oxide film containing molybdenum and / or phosphorus as an element, on the surface of the metal particles.

Here, the molybdenum-phosphorus coating is M
oO ₃ , Mo ₂ O ₃ , MoO, nAl ₂ O ₃ · mMoO ₃ , n
Al ₂ O ₃ · mMo ₂ O ₃ , nAl ₂ O ₃ · mMoO, P
_{2 O 5, nAl 2 O 3} · mP 2 O 5 (n, m is an arbitrary positive real number) is recommended to contain a compound having a composition represented by one or more members selected from the group consisting of.

Further, this molybdenum and / or phosphorus is an element and is 0.0 per 100 parts by mass of the metal particles.
It is desirable that the molybdenum-phosphorus coating be contained in the range of 1 to 5.0 parts by mass.

The colored metal pigment of the present invention comprises an oxide film or an oxynitride film containing one or more elements selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium on the outside of this cobalt film. It is recommended to have a second coating of

Here, the second coating is preferably made of an oxide layer or an oxynitride film containing titanium as an element. Also, this second coating is rutile, anatase, T
It is desirable to contain a compound having a composition represented by one or more selected from the group consisting of iO, Ti ₂ O ₃ and Ti ₃ O ₅ .

Further, the second coating has a thickness of 0.01-1 μm.
It is recommended to have a film thickness in the range of m. In addition, at least one element selected from the group consisting of titanium, zirconium, zinc, iron, chromium, and cerium is contained in the second coating within a range of 0.5 to 200 parts by mass with respect to 100 parts by mass of the metal particles. Is preferably contained in

The colored metallic pigment of the present invention is provided with a weather-resistant coating formed on the outside of this second coating, which is an oxide film containing one or more elements selected from the group consisting of aluminum, silicon and cerium. desirable.

Here, this weather resistant coating is made of Al ₂ O ₃ , Si.
It is recommended to contain a compound having a composition represented by one or more selected from the group consisting of O ₂ , SiO, CeO ₂ , and Ce ₂ O ₃ .

Further, the weather resistant coating has a thickness of 0.01 to 0.1.
It is preferable to have a film thickness in the range of μm. Further, one or more elements selected from the group consisting of aluminum, silicon and cerium are added to 100 parts by mass of the metal particles.
It is preferably contained in the weather resistant coating in an amount of 0.01 to 5 parts by mass.

It is recommended that the metal particles used in the colored metal pigment of the present invention are flake-shaped metal particles made of aluminum or aluminum alloy.

Further, the present invention includes a resin composition containing the above colored metal pigment and a resin.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by showing embodiments.

<Colored Metal Pigment> The colored metal pigment of the present invention is a colored metal pigment comprising metal particles and a single-layer or multi-layer coating for coating the surfaces of the metal particles. At least one layer of the multi-layer coating is a colored metal pigment, which is a cobalt coating formed of an anhydrous oxide film containing cobalt as an element.

<Metal Particles> The colored metal pigment of the present invention uses metal particles as base particles.

The material of the metal particles which are the base particles of the colored metal pigment of the present invention is not particularly limited, and aluminum, copper,
Zinc, titanium, iron, nickel, chromium and alloys thereof can be preferably used as the material. Among these materials, aluminum or aluminum alloy is particularly preferable because it is excellent in metallic luster and concealing power, is inexpensive, and has a low specific gravity, so that it is easy to handle.

The shape of the metal particles used in the present invention is not particularly limited, and may be various shapes such as granular, plate-like, lump-like, and flaky (scaly).
In order to give the coating film an excellent sense of brightness, it is preferably in the form of flakes.

When the metal particles used in the present invention are flaky, the average thickness of the metal particles is 0.01 μm.
It is preferably not less than the above, and more preferably not less than 0.02 μm. The average thickness of the metal particles is preferably 5 μm or less, more preferably 2 μm or less. Metal particles having an average thickness of less than 0.01 μm are not stably supplied industrially and tend to be difficult to obtain, and metal particles having an average thickness of more than 5 μm are also industrially stably supplied. This is because it tends to be difficult to obtain as well.

When the metal particles used in the present invention are flaky, the average particle size of the metal particles is preferably 2 μm or more, and more preferably 5 μm or more. Furthermore, the average particle size of the metal particles is 30.
It is preferably 0 μm or less, and particularly preferably 100 μm or less. Metal particles having an average particle size of less than 2 μm are not supplied industrially stably and tend to be difficult to obtain. Further, metal particles having an average particle size of more than 300 μm are also supplied industrially stably. This is because it tends to be difficult to obtain as well.

Further, when the metal particles used in the present invention are in the form of flakes, the shape factor, which is a value obtained by dividing the average particle diameter of the metal particles by the average thickness, is preferably 5 or more, and particularly 50. The above is more preferable. The shape factor is preferably 1000 or less, and more preferably 500 or less. This is because when the shape factor is less than 5, the metallic effect and the concealing property tend to be lowered, and when it exceeds 1000, the deformation and fracture tend to be increased in the dispersion step in the resin composition.

Further, when the metal particles used in the present invention are flakes, the interference color becomes clear if the shape of the metal particles is a coin shape having a smooth surface and rounded end faces. Therefore, it is more preferable.

When the metal particles used in the present invention are flake-shaped, the flake-shaped metal particles may be produced by a wet ball mill method (also known as the hall method) using powder or metal flakes obtained by the atomization method. A method of pulverizing using a dry ball mill method is preferable. Alternatively, a method may be used in which a metal thin film is vapor-deposited on a film made of a resin composition, peeled off, and then crushed by the above crushing method.

Here, the average particle size of the metal particles used in the present invention or the colored metal pigment described later is the particle size measured by a known particle size distribution measuring method such as a laser diffraction method, a micromesh sieve method and a Coulter counter method. The volume average is calculated from the distribution. The average thickness is calculated from the hiding power and density of metal particles or colored metal pigments.

Further, it is preferable that the surface of the metal particles used in the present invention is not adsorbed with a grinding aid added during grinding.

<Cobalt coating> The colored metal pigment of the present invention is a colored metal pigment comprising metal particles and a single-layer or multi-layer coating for coating the surfaces of the metal particles. At least one layer of the layer coating is a colored metal pigment, which is a cobalt coating formed of an anhydrous oxide film containing cobalt as an element.

As described above, by forming the cobalt coating formed of the anhydrous oxide film containing cobalt as an element on the outside of the metal particles, the metal particles can be colored in colors such as green, yellow and brown. Can be obtained.

Here, specific examples of the compound contained in the cobalt coating include CoO, Co ₂ O ₃ and Co.
₃ O ₄ , nCoO.mAl ₂ O ₃ , nCoO.mSiO
Examples thereof include compounds having a composition such as ₂ (n and m are arbitrary positive numbers). In addition, this cobalt coating may contain a small amount of metallic cobalt as long as the light transmittance of the cobalt coating is not impaired.

The thickness of the cobalt coating is 0.
It is preferably at least 01 μm, particularly 0.05 μm
The above is more preferable. Also, this film thickness is 1
It is preferably at most μm, more preferably at most 0.8 μm. When the film thickness is less than 0.01 μm, the colored metal pigment may not show a desired color, and when the film thickness exceeds 1 μm, the gloss of the colored metal pigment tends to decrease. Is.

The amount of the cobalt element contained in the cobalt coating is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of the metal particles as the base particles. Is more preferable. Furthermore, the amount of this cobalt element is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less. When the amount of this cobalt element is less than 0.5 parts by mass, a colored metal pigment having a desired color tends not to be obtained, and when the amount of this cobalt element exceeds 50 parts by mass, the gloss of the colored metal pigment is increased. Tends to decrease.

<Cobalt Film Forming Step> The method for forming a cobalt film consisting of an anhydrous oxide film containing a cobalt element on the outside of the metal particles used as the base particles of the colored metal pigment of the present invention is not particularly limited. However, for example, a cobalt compound is added to a suspension prepared by suspending metal particles or metal particles already coated with a single-layer or multi-layer coating in a hydrophilic solvent, and the suspension solution is added with a basic solution. While maintaining at, by stirring or kneading in a slurry state or paste state, to form a hydrated film containing cobalt element on the outside of the metal particles, and then heating to make the hydrated film an anhydrous oxide film, etc. Can be mentioned. In this method, since the hydrated film is changed to the anhydrous oxide film by heat treatment, a colored metal pigment with good color is obtained, and the adhesion between the colored metal pigment of the present invention and the binder resin contained in the paint is also improved. There is an advantage that the property is improved.

The cobalt compound used in the above method is not particularly limited, but examples thereof include cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt chloride, cobalt sulfate, cobalt naphthenate, cobalt oxalate, and cobalt citrate. 2, cobalt ethyl ethylhexanoate,
Examples thereof include cobalt gluconate, cobalt chromate, cobalt carbonate and the like. Among these cobalt compounds,
Particularly preferred compounds are cobalt nitrate, cobalt acetate and cobalt chloride.

Further, in the above case, the hydrophilic solvent used in the suspension is not particularly limited, but for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol. , N-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. The suspension may contain water.

In the above method, an amino compound is added to a suspension of metal particles or metal particles already coated with a single-layer or multi-layer coating to keep the pH in the basic range. While adsorbing the amino compound on the surface of the metal particles or the metal particles already coated with a single-layer or multi-layer coating, and then adding an aqueous solution in which a cobalt compound is dissolved and stirring by heating, the metal particles Alternatively, it is particularly preferable to deposit a cobalt hydrate film or a cobalt compound on the surface of the metal particles already coated with a single-layer or multi-layer coating, and finally heat-treat at a high temperature. Before the final heat treatment,
It is recommended that the paste containing the metal particles having a hydrated film be solid-liquid separated from the suspension in advance.

In the above case, the pH of the suspension
The amino compound used for adjusting the is not particularly limited, for example, monoethanolamine, diethanolamine, triethanolamine,
Ammonia, ethylenediamine, t-butylamine, γ
-Aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-
2-aminoethyl-3-aminopropylmethyldimethoxysilane, urea, O-aminobenzoic acid and the like can be mentioned.

In the above case, when the pH is kept in the basic range by adding the amino compound, the pH to be kept is preferably 7.0 or more, and particularly 8.0.
The above is more preferable. Also, this pH is 1
It is preferably 4.0 or less, and more preferably 10.0 or less. When the pH is less than 7.0, the cobalt compound may not be sufficiently deposited, and it is generally difficult to adjust the pH to a value higher than 14.0.

In the above case, when an aqueous solution in which a cobalt compound is dissolved is added and heated and stirred,
The temperature of the suspension is preferably 20 ° C or higher, and more preferably 50 ° C or higher. And, this temperature is preferably 120 ° C. or lower, and particularly 100 ° C.
The following is preferable. If the temperature is lower than 20 ° C, the cobalt compound tends not to be completely deposited, and if the temperature exceeds 120 ° C, the cobalt compound tends to deposit on a portion other than the surface of the base metal particles.

In the above case, when an aqueous solution in which a cobalt compound is dissolved is added and heated and stirred,
The heating and stirring time is preferably 5 minutes or longer, more preferably 30 minutes or longer. And, this time is preferably 10 hours or less, and particularly preferably 3 hours or less. If this time is less than 5 minutes, there is a tendency that the deposition of the cobalt compound does not completely occur, and if this time exceeds 10 hours, the deposition of the cobalt compound does not proceed further, which is economically disadvantageous. Tends to become.

In the above case, when the heat treatment is finally carried out at a high temperature after solid-liquid separation, the heat treatment temperature is preferably 250 ° C. or higher, and more preferably 350 ° C. or higher. . And this temperature is 700
The temperature is preferably not higher than 0 ° C, particularly preferably not higher than 650 ° C. If this temperature is below 250 ° C,
Since the water of crystallization does not evaporate sufficiently, color development tends to deteriorate, and if the temperature exceeds 700 ° C., aggregation of metal particles tends to occur.

In the above case, when the heat treatment is finally carried out at a high temperature, the heat treatment time is preferably 30 minutes or longer, and more preferably 1 hour or longer. And, this time is preferably 20 hours or less, and particularly preferably 10 hours or less.
When this time is less than 30 minutes, the color development of the colored metal pigment tends to be poor, and when this time exceeds 20 hours, the color tone of the obtained colored metal pigment tends to be dark.

<Silicon-Aluminum Coating> The colored metal pigment of the present invention is a silicon-based coating comprising an oxide film containing silicon and / or aluminum as an element inside a cobalt coating.
It is preferably provided with an aluminum coating.

In this way, by providing the silicon-aluminum film made of the oxide film containing silicon and / or aluminum as an element inside the cobalt film,
This is because the coloring effect of the cobalt coating is emphasized and the effect of preventing the reduction reaction of the oxide in the cobalt coating by the metal particles is obtained.

Specific examples of the compound containing silicon and / or aluminum contained in the silicon-aluminum coating as elements are Al ₂ O ₃ and SiO.
Examples thereof include compounds having a composition such as ₂ , SiO, nSiO ₂ .mAl ₂ O ₃ (n and m are arbitrary positive real numbers).

The thickness of the silicon-aluminum coating is preferably 0.01 μm or more, and more preferably 0.05 μm or more. Further, the film thickness is preferably 1 μm or less, and particularly preferably 0.
It is more preferably 5 μm or less. This film thickness is 0.
When the thickness is less than 01 μm, the color tone of the obtained colored metal pigment tends to be dark, and when the thickness exceeds 1 μm, the gloss of the colored metal pigment tends to decrease.

The amount of silicon and / or aluminum contained in the silicon-aluminum coating as an element is 100 parts by mass of metal particles which are base particles.
It is preferably 0.01 part by mass or more, and particularly 0.2
It is more preferable that the amount is at least parts by mass. Further, this amount is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less. This amount is 0.01
When it is less than 50 parts by mass, the color tone of the obtained colored metal pigment tends to be dark, and when this amount exceeds 50 parts by mass,
The luster of the colored metal pigment tends to decrease.

<Silicon-Aluminum Film Forming Step> As a method for forming a silicon-aluminum film composed of an oxide film containing silicon and / or aluminum as an element inside the cobalt film provided on the colored metal pigment of the present invention, Although not particularly limited, for example, silicon particles may be added to a slurry state or a paste state suspension in which metal particles or metal particles already coated with a single-layer or multi-layer coating are suspended in a hydrophilic solvent. By adding a compound and / or an aluminum compound and stirring or kneading while keeping the pH of the suspension basic or acidic, the surface of the metal particles or the metal particles already coated with a single-layer or multi-layer coating is added. A hydrated film containing silicon and / or aluminum as an element is formed and finally heat-treated at a high temperature to convert the hydrated film into an oxide film. How to it is preferred. Before the final heat treatment, solid-liquid separation of a paste containing metal particles having a hydrated film from the above suspension is recommended in advance.

The silicon compound and / or aluminum compound used in the above method is not particularly limited, but for example, methyltriethoxysilane,
Methyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane and the like, and condensates thereof, γ-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N- 2-aminoethyl-3-
Examples thereof include aminopropylmethyldimethoxysilane, sodium silicate, silicotungstic acid, silicomolybdic acid, triethoxyaluminum, trimethoxyaluminum, triisopropoxyaluminum, and the like, and condensates thereof, aluminum nitrate and the like.

Further, in the above case, the hydrophilic solvent used in the suspension is not particularly limited, but for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol. , N-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. The suspension may contain water.

In the above case, when the pH of the suspension is kept in the acidic range, the pH to be kept is preferably 1.0 or more, more preferably 2.0 or more. Further, this pH is preferably 5.0 or less, and more preferably 4.0 or less. This p
When H is less than 1.0, there is a tendency that the risk of a runaway reaction increases, and when this pH exceeds 5.0, silicon-aluminum formed of an oxide film containing silicon and / or aluminum as an element. This is because the coating tends to be insufficiently formed.

In the above case, when the pH of the suspension is kept in the basic range, the pH to be kept is preferably 7.0 or more, and more preferably 8.0 or more. . Further, this pH is preferably 14.0 or less, and more preferably 10.0 or less.
If the pH is less than 7.0, the silicon-aluminum coating composed of an oxide film containing silicon and / or aluminum as an element tends not to be sufficiently formed, and if the pH exceeds 14.0, the reaction is This is because the risk of runaway tends to increase.

In the above case, when the silicon compound and / or aluminum compound is added and stirred or kneaded, the temperature of the suspension is preferably 20 ° C. or higher, particularly 50 ° C. or higher. Is more preferable.
Then, this temperature is preferably 120 ° C. or lower, and particularly preferably 80 ° C. or lower. If this temperature is lower than 20 ° C, the desired thickness of the silicon-aluminum coating tends not to be obtained, and if this temperature exceeds 120 ° C, the silicon-aluminum coating tends not to deposit on the outside of the metal particles. is there.

In the above case, when the silicon compound and / or aluminum compound is added and stirred or kneaded, the stirring or kneading time is preferably 30 minutes or longer, and particularly preferably 1 hour or longer. Is more preferable. And, this time is preferably 50 hours or less, and particularly preferably 20 hours or less. If this time is less than 30 minutes, there is a tendency that film deposition does not sufficiently occur, and if this time exceeds 50 hours,
No further film deposition occurs, which tends to be economically disadvantageous.

<Molybdenum-Phosphorus Coating> The colored metal pigment of the present invention is provided with a molybdenum-phosphorus coating composed of an oxide film containing molybdenum and / or phosphorus as an element on the surface of the metal particles serving as the base particles. preferable.

By forming a molybdenum-phosphorus coating film made of an oxide film containing molybdenum and / or phosphorus as an element on the surface of the metal particles serving as the base particles, uniform deposition of the coating film formed thereon becomes easy. Because.
Moreover, since the molybdenum-phosphorus coating has corrosion resistance, an effect of preventing an abnormal reaction between the treatment solution and the metal particles can be obtained in the step of forming the next coating.

Here, specific examples of the compound containing molybdenum and / or phosphorus as elements contained in the molybdenum-phosphorus coating include MoO ₃ , Mo ₂ O ₃ ,
MoO, nAl ₂ O ₃ · mMoO ₃ , nAl ₂ O ₃ · mMo ₂
O ₃ , nAl ₂ O ₃ · mMoO, P ₂ O ₅ , nAl ₂ O ₃ · m
Examples thereof include compounds having a composition such as P ₂ O ₅ (n and m are arbitrary positive real numbers).

The amount of molybdenum and / or phosphorus contained as an element in the molybdenum-phosphorus coating is preferably changed according to the specific surface area of the metal particles used as the base particles. That is, it is preferable to increase the amount of molybdenum and / or phosphorus as an element for metal particles having a large specific surface area, and to increase the amount of molybdenum and / or phosphorus as an element for metal particles having a large specific surface area. It can be said that it is preferable to reduce the amount.

However, in a general case, the amount of molybdenum and / or phosphorus contained in the molybdenum-phosphorus coating as an element is 0.01 part by mass with respect to 100 parts by mass of the metal particles as the base particles. It is preferably not less than 1 part by mass, more preferably not less than 0.05 part by mass. Further, this amount is preferably 5.0 parts by mass or less, and particularly preferably 2.0 parts by mass or less. If this amount is less than 0.01 parts by mass,
It tends to be difficult to obtain the desired chemical stability,
If this amount exceeds 5.0 parts by mass, the color tone of the colored metal pigment (that is, metallic luster) is greatly reduced, the colored metal pigment aggregates, and the coating film physical properties such as moisture resistance, adhesion, and weather resistance are increased. There is a tendency for inconvenience such as decrease.

<Molybdenum-Phosphorus Film Forming Step> As a method for forming a molybdenum-phosphorus film consisting of an oxide film containing molybdenum and / or phosphorus as an element on the surface of the metal particles to be the base particles of the colored metal pigment of the present invention. Although not particularly limited, for example, an aqueous solution obtained by dissolving a molybdenum compound in hydrogen peroxide solution and / or a suspension in a slurry state or a paste state in which metal particles are suspended in a hydrophilic solvent and / or By adding a phosphorus compound and stirring or kneading, a hydrated film containing molybdenum and / or phosphorus as an element is formed on the surface of the metal particles,
A method in which the hydrated film is finally converted into an oxide film by heating at a high temperature is preferable. Before the final heat treatment, solid-liquid separation of a paste containing metal particles having a hydrated film from the above suspension is recommended in advance.

The molybdenum compound used in the above method is not particularly limited, but for example, the composition formula: Mo _x O _y .mH ₂ O ₂ .nH ₂ O (x is 1)
Or an integer of 2, y is an integer of 2 to 5, and m and n are arbitrary positive real numbers), such as polymolybdic acid peroxide, ammonium molybdate, and phosphomolybdic acid. The peroxidized polymolybdic acid can be prepared by dissolving metal molybdenum powder, molybdenum oxide or the like in an aqueous hydrogen peroxide solution (concentration: 5 to 40%).

The phosphorus compound used in the above method is not particularly limited, but for example,
Examples include orthophosphoric acid, phosphorous acid, hypophosphorous acid, phosphinic acid, pyrophosphoric acid, and polyphosphoric acid.

Further, in the above case, the hydrophilic solvent used in the suspension is not particularly limited, but for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol. , N-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. The suspension may contain water.

In the above case, when the aqueous solution of the molybdenum compound dissolved in hydrogen peroxide and / or the phosphorus compound is added and stirred or kneaded, the pH of the suspension is adjusted.
Is preferably 1.0 or more, and particularly preferably 2.0 or more. Further, this pH is preferably 10.0 or less, and more preferably 8.0 or less. This is because if the pH is less than 1.0 or more than 10.0, the metal particles tend to aggregate.

<Second coating> The colored metallic pigment of the present invention is an oxide film or oxynitride containing, outside the cobalt coating, one or more elements selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium. It is preferable to have a second coating formed of a film.

Thus, on the outside of the cobalt coating,
In addition, titanium, zirconium, zinc, iron, chromium,
By forming a second coating composed of an oxide film or an oxynitride film containing at least one element of cerium,
The color tone of the colored metal pigment can be further varied. Among these, an oxide film or an oxynitride film containing titanium as an element is particularly preferable because a good interference color is easily obtained.

Here, as a concrete example of the compound containing titanium as an element contained in the second coating,
Examples thereof include titanium oxides and titanium oxynitrides such as rutile, anatase, TiO, Ti ₂ O ₃ , and Ti ₃ O ₅ . Among these, rutile, TiO, Ti
Particularly preferred are titanium oxides such as ₂ O ₃ and Ti ₃ O ₅ and titanium oxynitrides.

Since a rutile type titanium oxide can be formed at a relatively low temperature by forming a hydrated film containing titanium as an element on the outer surface of the cobalt coating and heating it, a low melting point of aluminum or the like can be obtained. The second coating film containing rutile titanium oxide can also be formed in a colored metal pigment using metal particles made of metal as the base particles.

The thickness of this second coating is 0.01
It is preferably at least μm, more preferably at least 0.05 μm. Also, this film thickness is 1 μm
The thickness is preferably below, and particularly preferably 0.8 μm or below. When the film thickness is less than 0.01 μm, the colored metal pigment tends not to show a desired color, and when the film thickness exceeds 1 μm, the gloss of the colored metal pigment tends to be impaired. Because there is.

The amount of one or more elements selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium contained in the second coating is 100 parts by mass of the metal particles as the base particles. , 0.5 parts by mass or more, particularly preferably 1.0 parts by mass or more. Further, this amount is preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less. If this amount is less than 0.5 parts by mass, it tends to be difficult to obtain a colored metal pigment having pleochroism. If this amount exceeds 200 parts by mass, the gloss of the colored metal pigment tends to decrease. Because there is.

<Second Coating Forming Step> Titanium, zirconium, and
The method for forming the second coating formed of an oxide film or oxynitride film containing one or more elements selected from the group consisting of zinc, iron, chromium and cerium is not particularly limited, but for example, a cobalt coating In a slurry in which the pH is adjusted in a slurry state or a paste state in which metal particles having are suspended in a hydrophilic solvent, one or more selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium. While adding or stirring or kneading a compound containing an element, by hydrolyzing the compound, titanium, zirconium, zinc by depositing a hydrolyzate of the compound on the outer surface of the cobalt coating of the metal particles,
A method of forming a hydrated film containing one or more elements selected from the group consisting of iron, chromium and cerium, and finally performing heat treatment at a high temperature to form the hydrated film into an oxide film or an oxynitride film is preferable. Before the final heat treatment, solid-liquid separation of a paste containing metal particles having a hydrated film and a cobalt film from the above suspension is recommended in advance.

The compound containing titanium as an element used in the above method is not particularly limited, but examples thereof include titanium alkoxides, titanium chelate compounds, titanium coupling agents, titanium sulfate, titanium chloride and the like. Can be mentioned.

Specific examples of titanium alkoxides, titanium chelate compounds and titanium coupling agents include tetrabutoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, tetrakis (2-ethylhexoxy) titanium, and condensates thereof. , Tetrastearoxytitanium, diisopropoxybis (acetylacetonato) titanium,
Examples thereof include dibutoxybis (triethanolaminato) titanium, dihydroxybis (lactato) titanium, isopropyltri (N-aminoethylaminoethyl) titanate, and isopropyltris (dioctylpyrophosphate) titanate.

Among these compounds containing titanium as an element, tetrabutoxytitanium, tetraisopropoxytitanium, diisopropoxybis (acetylacetonato) titanium, dibutoxybis (triethanolaminato) titanium, dihydroxybis (lactato). Titanium, isopropyl tri (N-
Aminoethylaminoethyl) titanate is particularly preferred.

The compound containing zirconium, zinc, iron, chromium or cerium as an element used in the above method is not particularly limited, but for example,
Tetrabutyl zirconate, zirconium acylate,
Zirconium acetylacetonate, diethoxy zinc,
Dimethoxy zinc, zinc acetate, ferric nitrate, chromic acid, cerium acetate, etc. may be mentioned.

Further, in the above case, the hydrophilic solvent used in the suspension is not particularly limited, but for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol. , N-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. The suspension may contain water.

A second oxide film or oxynitride film containing one or more elements selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium is formed on the outside of the cobalt coating of the colored metal pigment of the present invention. As a method for forming a coating, specifically, titanium or zirconium is used while maintaining the pH of a suspension in a slurry state or a paste state in which metal particles having a cobalt coating are suspended in a hydrophilic solvent to be basic. , Zinc, iron, chromium, while adding a compound containing one or more elements selected from the group consisting of cerium, while stirring or kneading, by hydrolyzing the compound, to the outer surface of the cobalt coating of the metal particles One or more selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium by depositing a hydrolyzate of a compound. Element to form a hydrated film comprising, finally how to heat treatment at a high temperature in air or in a non-oxidizing atmosphere an oxide film or an oxynitride film hydration film is particularly preferred.

In the above method, it is recommended that the paste containing the metal particles having the hydrated film and the cobalt film be solid-liquid separated from the above suspension in advance before the final heat treatment. It Further, in the final high temperature heat treatment, a method of heating in a non-oxidizing atmosphere rather than in air is preferable. Furthermore, when forming an oxynitride film instead of an oxide film, a method of heating in an atmosphere containing ammonia or nitrogen is preferable.

In the above case, when the compound containing at least one element selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium is added and stirred or kneaded, the pH of the suspension is 7 It is preferably not less than 0.0, and more preferably not less than 8.0. Further, this pH is preferably 14.0 or less, and more preferably 10.0 or less. This is because if the pH is less than 7.0, the coating film tends not to be sufficiently formed, and if the pH exceeds 14.0, the risk of the reaction running away tends to increase.

In the above case, titanium,
When a compound containing one or more elements selected from the group consisting of zirconium, zinc, iron, chromium and cerium is added and stirred or kneaded, the temperature of the suspension is preferably 20 ° C. or higher, and particularly 30 It is more preferable that the temperature is not lower than ° C. The temperature is preferably 120 ° C. or lower, and particularly preferably 100 ° C. or lower. If the temperature is lower than 20 ° C, the film formation tends to be insufficient, and if the temperature exceeds 120 ° C, the film tends not to be uniformly deposited on the outside of the metal particles.

In the above case, titanium,
When a compound containing one or more elements selected from the group consisting of zirconium, zinc, iron, chromium and cerium is added and stirred or kneaded, the stirring or kneading time is preferably 30 minutes or more, and particularly 1 More preferably, it is at least the time. And, this time is preferably 50 hours or less, and particularly preferably 20 hours or less. If this time is less than 30 minutes, the film tends not to be sufficiently deposited, and if this time exceeds 50 hours, no further film is deposited, which is economically disadvantageous. is there.

In the above case, when the heat treatment is finally performed at a high temperature, the temperature of the heat treatment is preferably 250 ° C. or higher, and more preferably 350 ° C. or higher. And, this temperature is preferably 800 ° C. or lower, and particularly preferably 650 ° C. or lower. If the temperature is lower than 250 ° C, the coloration of the colored metal pigment tends to be poor, and if the temperature exceeds 800 ° C, the colored metal pigment tends to aggregate.

In the above case, when the heat treatment is finally performed at a high temperature, the heat treatment time is preferably 30 minutes or longer, and more preferably 1 hour or longer. And, this time is preferably 10 hours or less, and particularly preferably 5 hours or less. If this time is less than 30 minutes, the color development of the colored metal pigment tends to deteriorate, and if this time exceeds 10 hours,
Agglomeration of metal particles tends to occur and the color tone of the colored metal pigment tends to be dark.

<Weatherproof Coating> When the colored metal pigment of the present invention has a second coating, an oxide film containing one or more elements selected from the group consisting of aluminum, silicon and cerium is provided outside the second coating. It is preferable to provide the following weather resistant coating.

Here, when the colored metal pigment of the present invention has a second coating consisting of an oxide film or an oxynitride film containing titanium as an element, the group consisting of aluminum, silicon and cerium is provided outside the second coating. It is particularly preferable to provide a weather-resistant coating film made of an oxide film containing one or more elements selected from the above.

In this way, on the outer side of the second film made of the oxide film or the oxynitride film containing titanium as an element,
Aluminum, silicon, by forming a weathering coating consisting of an oxide film containing one or more elements selected from the group consisting of cerium, it is possible to reduce the photocatalytic activity of titanium compounds including titanium oxide,
This is because it is possible to prevent discoloration of the coating film by the coating material containing the colored metal pigment of the present invention, and it is possible to improve the weather resistance.

Here, as a specific example of the compound containing at least one element selected from the group consisting of aluminum, silicon and cerium contained in the weather resistant coating, Al ₂
Examples thereof include compounds having a composition such as O ₃ , SiO ₂ , SiO, CeO ₂ , and Ce ₂ O ₃ .

The thickness of this weather resistant coating is 0.01
It is preferably at least μm, more preferably at least 0.02 μm. Also, this film thickness is 0.5
It is preferably not more than μm, and particularly preferably not more than 0.2 μm. If the film thickness is less than 0.01 μm, the photocatalytic activity of the titanium compound tends to be insufficiently suppressed, and if the film thickness exceeds 0.5 μm, the gloss of the colored metal pigment is impaired. This is because it tends to occur.

Further, the amount of one or more elements selected from the group consisting of aluminum, silicon and cerium contained in this weather resistant coating is 0.01 parts by mass or more based on 100 parts by mass of the metal particles as the base particles. Is preferable, and more preferably 0.1 part by mass or more. Further, this amount is preferably 5.0 parts by mass or less, and particularly preferably 2.0 parts by mass or less.
If this amount is less than 0.01 part by mass, the photocatalytic activity of the titanium compound may not be sufficiently suppressed, and if this amount exceeds 5.0 parts by mass, the gloss of the colored metal pigment tends to decrease. There is.

<Weatherproof Film Forming Step> A method of forming a weatherproof film consisting of an oxide film containing one or more elements selected from the group consisting of aluminum, silicon and cerium on the outside of the second film of the colored metal pigment of the present invention. Although not particularly limited, as a method for forming a weather-resistant coating film made of an oxide film containing one or more elements selected from the group consisting of aluminum and silicon, among these methods, for example,
A method similar to the above-mentioned silicon-aluminum film forming step is preferable.

Of the above methods, as a method for forming a weather resistant coating made of an oxide film containing cerium as an element, for example, metal particles having a cobalt coating and a second coating are suspended in a hydrophilic solvent. Add a cerium compound to the slurry or paste suspension,
By heating and stirring or kneading while maintaining the pH of the suspension basic, a hydrated film containing cerium as an element is formed on the surface of the second coating having metal particles, and finally heat-treated at high temperature. A method of converting the hydrated film into an oxide film is preferable. Before the final heat treatment, solid-liquid separation of a paste containing metal particles having a hydrated film from the above suspension is recommended in advance.

The cerium compound used in the above method is not particularly limited, but examples thereof include cerium acetate, cerium nitrate, and cerium alkoxide.

Furthermore, in the above case, the hydrophilic solvent used in the suspension is not particularly limited, but for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol. , N-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone and the like. The suspension may contain water.

In the above case, when the cerium compound is added and the mixture is heated and stirred or kneaded with heat, the pH of the suspension is preferably 7.0 or more, and particularly, 8.
It is more preferably 0 or more. Also, this pH is 1
It is preferably 4.0 or less, and more preferably 10.0 or less. If this pH is less than 7.0, there is a tendency that the film is not sufficiently formed.
This is because if the value exceeds 14.0, there is a tendency that the reaction becomes runaway.

<Resin Composition> The resin composition of the present invention is a resin composition containing the colored metal pigment of the present invention and a resin. In the present specification, when described as a resin composition, it includes a paint and a coating film thereof, an ink and a coating film thereof, and a resin composition molded body obtained by injection molding or the like.

The colored metal pigment of the present invention can be suitably blended with a binder resin in a resin composition such as a paint or an ink. Here, the resin composition such as a coating material and an ink with which the colored metal pigment of the present invention is blended may be of any type such as an organic solvent type, an aqueous type or a powder coating material. And, the colored metal pigment of the present invention, among these various types of resin compositions,
It is used by being particularly suitably blended with an aqueous resin composition such as an aqueous paint or an aqueous ink.

Further, the content of the colored metal pigment of the present invention in the resin composition of the present invention is preferably 0.1% by mass or more, and particularly preferably 1.0% by mass or more. Further, the blending amount is preferably 30% by mass or less, and particularly preferably 20% by mass or less. If this blending amount is less than 0.1% by mass, a sufficient metallic feeling tends not to be obtained, and if this blending amount exceeds 30% by mass, the weather resistance, corrosion resistance, and
This is because the physical properties such as mechanical strength may be adversely affected.

The resin contained in the resin composition of the present invention is not particularly limited, and resins generally used as binders in resin compositions such as paints and inks can be preferably used. Examples thereof include acrylic resin, alkyd resin, polyester resin, polyurethane resin, polyvinyl acetate resin, nitrocellulose resin, and fluororesin.

The resin composition of the present invention may contain water, an organic solvent and the like. Furthermore, the resin composition of the present invention contains, in addition to the colored metal pigment and resin of the present invention, a pigment, an additive or the like, if necessary, within a range not impairing the characteristics of the resin composition of the present invention. Good.

Here, the pigment which can be blended in the resin composition of the present invention is not particularly limited, but for example, phthalocyanine, quinacridone, isoindolinone, perylene, azo lake, iron oxide, yellow lead, Examples thereof include carbon black, titanium oxide, pearl mica, other extender pigments, coloring pigments and dyes.

The additives that can be added to the resin composition of the present invention are not particularly limited, and examples thereof include surfactants, curing agents, ultraviolet absorbers, static eliminators and thickeners. And so on.

Further, the material of the base material when the resin composition of the present invention is applied as a paint or an ink is not particularly limited, and examples thereof include paper, wood, cloth, plastic,
A base material made of metal or the like can be used. By appropriately selecting the type and composition of the binder resin blended in the resin composition of the present invention, it is possible to suitably coat any base material.

Further, when the resin composition of the present invention is used as a paint or an ink, it may be directly coated on a substrate, but an undercoat layer or an intermediate coat layer may be provided on the substrate by electrodeposition coating or the like. May be painted on.

When the resin composition of the present invention is used as a paint or ink, a coating film made of the resin composition of the present invention may be used as the outermost layer. A top coat layer may be formed on.

[0129]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1 First, hydrogen peroxide 30% (w
/ V) containing 3 g of molybdenum powder to 3 g of hydrogen peroxide solution, and reacting the resulting solution with isopropyl alcohol (hereinafter abbreviated as IPA) 200
g, and the solution was further added to commercially available aluminum particles (manufactured by Toyo Aluminum Co., Ltd., 5422NS, solid content 7).
5% (w / w), average particle size 19 μm, average thickness 1 μm)
40 g (30 g as aluminum content) was added to form a slurry, and the mixture was stirred and mixed at 75 ° C. for 1 hour.

Then, monoethanolamine was added to the above slurry to adjust the pH value of the slurry to 10.0. Cobalt (II) acetate 4 in pH adjusted slurry
Dissolve 15 g of hydrate in 40 g of water and add
The mixture was stirred and mixed at 0 ° C for 2 hours.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment (almost no color) was heat-treated in air at 500 ° C. for 3 hours. The aluminum pigment after the heat treatment had a yellowish green color and had an excellent metallic feel.

Example 2 To the slurry obtained by dispersing 30 g of the aluminum pigment obtained in Example 1 in 200 g of IPA was added 12 g of tetrabutoxytitanium, 0.5 g of monoethanolamine and 10 g of water, and the mixture was stirred at 75 ° C. for 2 hours. Mix and react.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was heat-treated at 600 ° C. for 3 hours in an argon atmosphere. The aluminum pigment after the heat treatment had an appearance of changing from pink to gold depending on the viewing angle, and had an excellent metallic appearance.

<Example 3> Phosphoric acid (active ingredient 98% (w
/ W)) 0.3 g of isopropyl alcohol (hereinafter IP
Dissolved in 200 g of A, and further commercially available aluminum particles (manufactured by Toyo Aluminum Co., Ltd., 5422N)
S) (40 g (30 g as aluminum content)) and ethylenediamine were added to adjust the pH value of the slurry to 10.0, and the mixture was stirred and mixed at 75 ° C. for 1 hour.

Thereafter, cobalt nitrate (I
10 g of I) .hexahydrate was dissolved in 40 g of IPA and added, and the mixture was further stirred and mixed at 75 ° C. for 2 hours.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment (almost no color) was heat-treated in air at 300 ° C. for 3 hours. The aluminum pigment after the heat treatment had a pale yellow color and had an excellent metallic feel.

Example 4 In a slurry prepared by dispersing 30 g of the aluminum pigment obtained in Example 3 in 200 g of IPA, 12 g of tetraisopropoxytitanium, 1.5 g of dibutoxybis (triethanolaminato) titanium,
10 g of water was added, and the mixture was stirred and mixed at 75 ° C. for 2 hours to cause a reaction.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was heat-treated at 600 ° C. for 3 hours in an argon atmosphere. The aluminum pigment after the heat treatment had an appearance of changing from blue to purple depending on the viewing angle and had an excellent metallic appearance.

<Example 5> 0.6 g of phosphomolybdic acid was dissolved in 200 g of dipropylene glycol monomethyl ether, and 40 g of commercial aluminum particles (5422NS, manufactured by Toyo Aluminum Co., Ltd.) (30 g as aluminum content) was added. The mixture was stirred and mixed at 90 ° C. for 1 hour.

Then, γ-aminopropyltriethoxysilane was added to the above slurry to adjust the pH value of the slurry to 9.5.

Cobalt oxalate (I
30 g of I) dihydrate was dissolved in 40 g of water and added, and the mixture was further stirred and mixed at 90 ° C. for 2 hours. After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment (almost no color) was heat-treated in air at 300 ° C. for 3 hours. Aluminum pigment after heat treatment shows green,
It had an excellent metallic feel.

Example 6 30 g of the aluminum pigment obtained in Example 5 was dispersed in 200 g of ethyl alcohol to prepare a slurry, and 18 g of tetrabutoxycytitanium was added to the slurry.
% (W / v) aqueous ammonia solution (3 g) and added at 75 ° C for 2
The mixture was agitated and mixed for a reaction time.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in nitrogen at 600 ° C.
And heat treated for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from green to brown depending on the viewing angle, and had an excellent metallic appearance.

Example 7 Polyphosphoric acid was dissolved in 200 g of isopropyl alcohol, and commercially available aluminum particles (manufactured by Toyo Aluminum Co., Ltd., 5422NS) were added.
0 g (30 g as aluminum content) was added, and the mixture was stirred and mixed at 50 ° C. for 1 hour. Thereafter, monoethanolamine was added to the above slurry to adjust the pH value of the slurry to 8.5.

40 g of triisopropoxyaluminum (hereinafter abbreviated as TEOS) was added to the pH-adjusted slurry, and the mixture was further stirred and mixed at 50 ° C. for 10 hours. The pH value of the slurry was checked every 2 hours on the way, and the pH value was adjusted to 8.5 by adding monoethanolamine.

Then, cobalt acetate (I
I) .4 hydrate (5 g) was added, and the mixture was stirred and mixed at 75 ° C for 2 hours. After completion of the reaction, the slurry is separated into solid and liquid by a filter,
The obtained aluminum pigment was heat-treated in nitrogen at 300 ° C. for 3 hours. The aluminum pigment after the heat treatment had a beige color and had an excellent metallic feel.

Example 8 To a slurry prepared by dispersing 30 g of the aluminum pigment obtained in Example 7 in 200 g of IPA was added 30 g of tetrabutoxytitanium, 3 g of triethanolamine and 15 g of water, and the mixture was stirred and mixed at 75 ° C. for 2 hours. , Reacted.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in air at 500 ° C.
And heat treated for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from light green to pink depending on the viewing angle and had an excellent metallic appearance.

Example 9 To a slurry prepared by dispersing 30 g of the aluminum pigment obtained in Example 8 in 200 g of IPA was added 5 g of tetraethoxysilane and 15 g of 10% (w / v) ammonia aqueous solution, and the mixture was heated at 75 ° C. for 5 hours. Mix with stirring,
It was made to react.

After the completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was mixed in a nitrogen atmosphere at 6
It heat-processed at 00 degreeC for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from light green to pink depending on the viewing angle and had an excellent metallic appearance.

Example 10 To a slurry prepared by dispersing 30 g of the aluminum pigment obtained in Example 8 in 200 g of water was added 4.5 g of aluminum nitrate and 15 g of a 10% (w / v) ammonia solution, and the mixture was stirred at 75 ° C. for 5 hours. The mixture was stirred and mixed for a reaction time to react.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was heat-treated at 600 ° C. for 3 hours in an argon atmosphere. The aluminum pigment after the heat treatment had an appearance of changing from light green to pink depending on the viewing angle and had an excellent metallic appearance.

Example 11 30 g of the aluminum pigment obtained in Example 8 was dispersed in 200 g of water to prepare a slurry, and 5 g of cerium (III) acetate monohydrate and 10% (w / w) were added.
v) 15 g of aqueous ammonia solution was added, and the mixture was stirred and mixed at 75 ° C. for 5 hours to react.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was 550 ° C. in air.
And heat treated for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from light green to pink depending on the viewing angle, and had an excellent metallic feel.

Example 12 To 200 g of dipropylene glycol monomethyl ether was added 40 g of commercially available aluminum particles (5422NS, manufactured by Toyo Aluminum Co., Ltd.).
(30 g as aluminum content) and monoethanolamine were added to adjust the pH value of the slurry to 10.0.

[0157] Cobalt acetate (I
15 g of I) tetrahydrate was dissolved in 40 g of water and added, and the mixture was further stirred and mixed at 75 ° C. for 2 hours. The aluminum particles reacted in the slurry on the way, and a large amount of hydrogen gas was generated to finally become a brown slurry.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was mixed with 200 g of IPA.
Tetrabutoxy titanium 3
0 g, triethanolamine 3 g and water 15 g were added,
The mixture was stirred and mixed at 5 ° C. for 2 hours to be reacted.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in nitrogen at 600 ° C.
And heat treated for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from red to orange depending on the viewing angle, and had an excellent metallic feel.

Comparative Example 1 Commercially available aluminum particles (Toyo Aluminum Co., Ltd., 5422NS) were washed with acetone, suction filtered, and dried at 50 ° C. for 2 hours. 30 g of aluminum particles were dispersed in 300 g of n-butanol. To the slurry, 15 g of tetrabutoxytitanium was added, and further, a solution of 7.5 g of water dissolved in 50 g of n-butanol was gradually added, and the mixture was reacted at 75 ° C. for 1 hour.

After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in air at 250 ° C.
And heat treated for 15 minutes. The aluminum pigment after the heat treatment had almost no silver color. Further, in the powder containing the aluminum pigment after the heat treatment,
Coarse particles of agglomerates due to the reaction between water and aluminum were mixed.

Comparative Example 2 Cobalt (II) nitrate hexahydrate 60 g, oxalic acid 30 g, iron-EDTA-chelate 45
g was dissolved in 1000 g of water, and triethanolamine 12 was added.
0 g and 1N sodium hydroxide solution were added to adjust the pH value to 7.
A solution adjusted to 3 was prepared.

To this solution, commercially available aluminum particles (Toyo Aluminum Co., Ltd., 5422NS) were washed with acetone, suction filtered, and dried at 50 ° C. for 2 hours. 30 g of aluminum particles and 500 g of ethanol were added, and the mixture was heated at 85 ° C. After heating for 10 minutes, generation of hydrogen gas was observed during the treatment due to the reaction between the treatment liquid and the aluminum pigment.

After adding 5000 g of water to this slurry,
Solid-liquid separation was performed with a filter. A beige powder was mixed in the obtained aluminum pigment, but the aluminum pigment itself had almost no color. Further, in the powder containing the aluminum pigment, large agglomerates formed by the reaction of water and aluminum were mixed.

Comparative Example 3 Commercially available aluminum particles (Toyo Aluminum Co., Ltd., 5422NS) were washed with acetone, suction filtered, and dried at 50 ° C. for 2 hours. 30 g of aluminum particles were dispersed in 300 g of IPA to obtain a slurry. 120 g of water, 25% (w / v) aqueous ammonia solution 1
0 g was added and heated to 60 ° C.

Then, 90 g of tetraethoxysilane was added to IP.
A solution dissolved in 120 g was gradually added over 3 hours,
Then, it was made to react at 55 degreeC for 14 hours. During the treatment process, a large amount of hydrogen gas was generated due to the reaction of the aluminum particles with the treatment liquid. After completion of the reaction, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in air for 8
It was dried at 0 ° C. for 3 hours.

The powder containing the aluminum pigment after the heat treatment contained a large agglomerate formed by the reaction of water and aluminum, and this was passed through a 45 μm sieve, and 20 g of the obtained powder was again charged with 200 g of IPA. Dispersed. 10 g of tetrabutoxytitanium, 2 g of triethanolamine and 10 g of water were added to this slurry, and the mixture was stirred and mixed at 75 ° C. for 2 hours to cause a reaction.

After the reaction was completed, the slurry was subjected to solid-liquid separation with a filter, and the obtained aluminum pigment was placed in nitrogen at 600 ° C.
And heat treated for 3 hours. The aluminum pigment after the heat treatment had an appearance of changing from beige to orange depending on the viewing angle, but it was an aluminum pigment having many aggregates and not having a metallic appearance.

<Preparation of Aqueous Metallic Base Paint> Using the aluminum pigments obtained in Examples 1 to 12 and Comparative Examples 1 to 3, an aqueous metallic base paint was prepared with the following formulation. As the aluminum pigment, the aluminum pigment after the final heat treatment was used. In addition, the aluminum pigments obtained in Comparative Examples 1 to 3 have a pore size of 4
An aluminum pigment passed through a 5 μm sieve was used.

[0170]   [Composition of water-based metallic base paint] Water-soluble acrylic resin (* 1) 28.2g Melamine resin (* 2) 4.4g Triethanolamine 1.1g Deionized water 44.8g Isopropyl alcohol 3.0g Aluminum pigment (* 3) 3.0 g as solid content In the above formulation, each symbol is * 1: Almatex WA911 manufactured by Mitsui Chemicals, Inc. * 2: Cymel 350 manufactured by Mitsui Chemicals, Inc. * 3: Aluminum pigments obtained in Examples 1 to 12 or Comparative Examples 1 to 3 Shall be represented.

<Preparation of Coated Plate> For the test, the above-mentioned water-based metallic base paint prepared by using the aluminum pigments obtained in Examples 1 to 12 or Comparative Examples 1 to 3 was electrodeposited with a primary rust preventive paint in advance. 13μ dry film thickness on steel plate
m by air spray coating and then pre-drying at 90 ° C for 10 minutes, and then an organic solvent type topcoat paint with the following composition is air spray coated to a dry film thickness of 40 μm and at 130 ° C. A metallic coated plate was prepared by drying for 30 minutes.

[0172]   [Compounding of organic solvent type top coat paint]   Acrylic resin (* 1) 140g   Melamine resin (* 2) 50g   Solvesso 100 60g In the above formulation, each symbol is * 1: Almatex 110 manufactured by Mitsui Chemicals, Inc. * 2: Uban 20SE60 manufactured by Mitsui Chemicals, Inc. Shall be represented.

<Performance Evaluation> Obtained as described above,
Regarding the metallic paint coated plate containing the aluminum pigment obtained in Examples 1 to 12 or Comparative Examples 1 to 3 in the coating film,
The appearance, hue, saturation, polychromaticity (the property that the hue changes depending on the observation angle), and metallic feeling of the coating film of each coated plate were evaluated according to the following evaluation methods. Table 1 shows the obtained evaluation results.

(I) Evaluation method of appearance of coating film The appearance of the coating film of the metallic coated plate was visually observed,
It evaluated according to the following evaluation criteria. 5: Surface is very smooth 4: Surface is smooth 3: Surface has waviness, but gloss 2: Surface has fine irregularities 1: Surface is rough (ii) Evaluation method of hue of coating film Metallic coating The hue of the coating film on the coated plate was visually observed while changing the observation angle, and the observed color or the state of the change in color was evaluated.

(Iii) Evaluation Method of Saturation of Coating Film The saturation of the coating film of the metallic coated plate was measured by a color difference meter (SM-6-CH type manufactured by Suga Test Instruments Co., Ltd.) to obtain a c value (= (a ² +
b ² ) ^1/2 ) was measured and evaluated according to the following evaluation criteria. 5: 20 ≦ c 4: 15 ≦ c <20 3: 10 ≦ c <15 2: 5 ≦ c <10 1: c <5 (iv) Method for evaluating multicolor of coating film Metallic coating Visually observe the appearance,
It evaluated according to the following evaluation criteria. 5: The hues of the color in the specular reflection direction and the color in the diffuse reflection direction change significantly 4: The hues of the color in the specular reflection direction and the color in the diffuse reflection direction change in the same system hue 3: The color in the specular reflection direction The hue of the color in the diffuse reflection direction is the same, and the lightness changes. 2: The color in the specular reflection direction and the color in the diffuse reflection direction slightly change in hue or lightness. 1: The color in the specular reflection direction and the color in the diffuse reflection direction. Color hardly changed (v) Evaluation method of metallic feeling of coating film The appearance of the coating film of the metallic coating plate was visually observed,
It evaluated according to the following evaluation criteria. 5: There is a metallic feeling equivalent to the case of using untreated aluminum particles 4: A little inferior to the case of using untreated aluminum particles, but there is a metallic feeling 3: When using untreated aluminum particles Although it is considerably inferior, it has a metallic feeling for the time being 2: Metallic feeling is greatly reduced as compared with the case of using untreated aluminum particles 1: Almost no metallic feeling (vi) Evaluation of weather resistance of coating film Method Apply a metallic coating plate to a QUV accelerated weather resistance tester (Q-
PANEL COMPANY, QUV / SE type)) for 1000 hours, and the change in the color difference of the coated plate before and after the test is measured by a color difference meter (SM-6-CH, manufactured by Suga Test Instruments Co., Ltd.).
The weather resistance of the coating film was evaluated by measuring the type. It can be said that the smaller the change in color difference, the better the weather resistance of the coating film.

[0176]

[Table 1]

From the results shown in Table 1, the coating films of the metallic coated plates using the aluminum pigments obtained in Examples 1 to 12 of the present invention were the aluminum pigments obtained in Comparative Examples 1 to 3. Compared with the coating film of metallic paint coated plate,
It can be seen that the appearance, saturation, polychromaticity, metallic feel, and weather resistance of the coating film are remarkably excellent.

Further, from the results shown in Table 1, the coating films of the metallic coated plates using the aluminum pigments obtained in Examples 1 to 12 of the present invention include a color having a hue which changes depending on the viewing angle. You can see that they are colored in various hues.

The embodiments and examples disclosed this time must be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0180]

From the above results, the colored metal pigment of the present invention can realize various hues including hues having hues that change depending on the viewing angle, and the finished appearance, saturation, and polychromaticity. It can be said that it is a colored metal pigment which is excellent in metallic feeling and weather resistance and can be manufactured by a safe and simple manufacturing method.

Further, since the resin composition of the present invention contains the colored metal pigment of the present invention and the resin, it is possible to realize various hues including hues having hues that change depending on the viewing angle. It can be said that the resin composition is excellent in finished appearance, saturation, polychromaticity, metallic feeling and weather resistance, and can be manufactured by a safe and simple manufacturing method.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AB021 BD121 BF021 BG021                       CF011 CF211 CK021 DA086                       DA096 DA106 DA116 FB076                       FD096                 4J037 AA04 CA09 CA12 CA21 CA23                       EE03 EE04 FF03

Claims (7)

[Claims] 1. A colored metal pigment comprising metal particles and a single-layer or multi-layer coating for coating the surface of the metal particles, wherein at least one layer of the single-layer or multi-layer coating contains cobalt. A colored metal pigment, which is a cobalt coating formed of an anhydrous oxide film containing an element. 2. The colored metal pigment according to claim 1, further comprising a silicon-aluminum coating formed of an oxide film containing silicon and / or aluminum as an element inside the cobalt coating. 3. The molybdenum-phosphorus coating film made of an oxide film containing molybdenum and / or phosphorus as an element is provided on the surface of the metal particles.
Or the colored metal pigment according to 2. 4. A second coating formed of an oxide film or an oxynitride film containing one or more elements selected from the group consisting of titanium, zirconium, zinc, iron, chromium and cerium is provided outside the cobalt coating. The colored metal pigment according to any one of claims 1 to 3, which is characterized in that. 5. The colored metal pigment according to claim 4, wherein the second coating is made of an oxide film or an oxynitride film containing titanium as an element. 6. Aluminum on the outside of the second coating,
The colored metal pigment according to claim 5, further comprising a weather resistant coating formed of an oxide film containing one or more elements selected from the group consisting of silicon and cerium. 7. A resin composition containing the colored metal pigment according to claim 1 and a resin.